In situ TEM heating experiments at temperatures between 820° and 860°C provide significant insights into the atomistics of neck formation during the sintering of nanoscale faceted, single‐crystal particles of ZrO2. High‐resolution TEM was used to observe the crystallography and the relative orientation in a variety of original particle‐pairs and the relative orientation of their evolving necks. Previous studies have determined that unconstrained particles can rotate during neck growth. When there is a significant amount of misalignment, the particles are not able to align completely. In these instances, the neck that forms is epitaxial with one of the particles. Additionally, in particle‐pairs with significant misalignment, the neck stops growing when it forms a crystallographic facet which is continuous with the preexisting facet of the template particle. When the two particles have close to the same orientation, the particles rotate into complete alignment and the neck that forms is consequently epitaxial with both particles. When the neck‐particle system is in complete registry, the growing neck is rounded: there is an aperiodic arrangement of steps, even on the atomic resolution scale. The experimental results are discussed in terms of the random starting state of the two particles, the equilibrium crystal shape of the particle‐neck system, and the operative kinetic mechanisms.